F and cosmetic resin and compositions therefor dyeing keratinous fibers and setting hair with indamines salts thereo

ABSTRACT

THE INVENTION PERTAINS TO INDAMINES AND SALTS THEREOF WHICH ARE USEFULLY EMPLOYED IN A DYE COMPOSITION FOR COLORING KERATINOUS FIBERS, ESPECIALLY HUMAN HAIR AND IN HAIR SETTING LOTIONS WHICH ALSO INCLUDES A FILM-FORMING COSMETIC RESIN.

United States Patent Office 3,758,268 Patented Sept. 11, 1973 3,758,268 DYEING KERATINOUS FIBERS AND SETTING HAIR WITH INDAMINES, SALTS THEREOF AND COSMETIC RESIN AND COMPOSITIONS THEREFOR Gregoire Kalopissis, Paris, Andree Bugaut, Boulogne-sur- Seine, and Francoise Estradier, Paris, France, asslgnors to Societ Anonyme dite: LOreal, Paris, France No Drawing. Continuation-impart of application Ser. No. 52,739, July 6, 1970, now Patent No. 3,677,690. This application July 12, 1971, Ser. No. 161,887 Claims priority, application Luxembourg, July 17, 1969, 59,119; July 17, 1970, 61,354; Jan. 15, 1971, 62,426, The portion of the term of the patent subsequent to July 18, 1989, has been disclaimed Int. Cl. D06p 3/04 US. Cl. 8-11 21 Claims ABSTRACT OF THE DISCLOSURE The invention pertains to indamines and salts thereof which are usefully employed in a dye composition for coloring 'keratinous fiber's, especially human hair and in hair setting lotions which also includes a film-forming cosmetic resin.

wherein R R R and R each represent hydrogen, halogen, lower alkyl having 1-4 carbon atoms and lower alkoxy containing from 1 to 4 carbon atoms, and R represents hydrogen or lower alkyl having 1-4 carbon atoms. This formula does not exclude the tautomeric forms.

The novel indamines of this invention can be prepared by condensing a paraphenylenediamine having the formula:

/3 2 HzN 4 5 6 1 -Nm wherein R R R and R have the meanings indicated above, on a 6-hydroxy phenomorpholine having the formula:

N gym-H wherein R has the meaning given above. Said paraphenylene diamine and/ or 6-hydroxy phenomorpholine can also be in the form of a salt such as hydrochloride, hydrobromide or sulfate. This condensation reaction can be per- I stoichiometric requirements. The reaction medium can be made alkaline, preferably by the addition thereto of ammonia, although other alkalinizing agents such as NaOH and KOH can also be employed.

The paraphenylenediamine used in the preparation of the indamines according to the present invention can be, for example, paraphenylenediamine, paratolylenediamine, 2,5-diamino anisole, 2,5-diamino chlorobenzene, 2-mothoxy S-methyl paraphenylenediamine, 2,6-dimethyl 3-1'nethoxy paraphenylenediamine and 1,4 diamino durene. The mole ratio of paraphenylenediamine to the 6-hydroxy phenomorpholine in the condensation reaction can vary between about 3:1 to 0.5 :1 and preferably between 1:1 to 2:1.

The novel indamines of the present invention constitute dyes that have a particularly interesting application in dyeing keratinous fibers, particularly human hair.

Thus, an object of thepresent invention is the provision of a novel coloring agent useful in a dyeing composition for keratinous fibers, characterized by the fact that said coloring agent comprises at least one indamine defined above. p

When the dyeing composition of the present invention contains as the sole dyeing agent, one or more indamines described above, the coloration imparted to the keratinous fibers by its use varies from blue to green and from green to blond. The obtained colorations impart glints and very often a pearly glance to the keratin fiber.

However, the dye composition of this invention can also include, in addition to the indamines defined above other dyes ordinarily used for dyeing hair. Representative of such other dyes are, for example, azo, aniline, anthraquinone, azine, oxazine dyes and "nitroderivatives of the benzene series. Further, indoanilines, indophenols or indamines other than those defined above can also be used.

The novel compositions of this invention comprise an aqueous or aqueous alcoholic solution of the said indamine, which compositions can be prepared by dissolving in said aqueous or aqueous alcoholic medium one or more of said indamines and, if desired, one or more conventionally employed dyes useful in the coloration of keratin fibers. Additionally, however, the composition of this invention can also contain thickeners and thus be in the form of a cream or gel.

Furthermore, the composition of the present invention can also contain various conventional ingredients usually employed in cosmetic preparations, for example, wetting agents, dispersing agents, swelling agents, penetration agents, softeners or perfumes. It has also been found that V the composition of this invention can be in the form of ,a sprayable aerosol, packaged in a conventional aerosol bomb or can.

When the composition of the present invention is em? ployed as a hair dye composition the pH of the hair dye composition can vary within broad limits and will range generally between about 4-11, and preferably between 7-11. The amount of indamine present in the aqueous or aqueous alcohol solution comprising the dye composition can vary, for instance, depending on the particular indamines present, the color desired, as well as the color of the hair to be dyed. Thus an amount of the indamine effective to produce the desired coloration is employed.

Generally this amount ranges between about 0.002 to 1 weight percent of the total aqueous or aqueous alcohol solution and, preferably, between about (LOGS-0.5% by weight.

Dyeing of keratinous fibers, in particular human hair, with the dyeing composition of this invention is performed in accordance with conventional dyeing techniques, for instance, by applying the said composition to the fibers to be dyed, permitting the composition to remain in contact with said fibers for a period of about -30 minutes and thereafter, rinsing and, if desired, washing, and drying the fibers.

The novel indamines of this invention can also be employed to provide a novel hair setting lotion comprising an admixture of at least one of said indamines defined above and a dilute alcohol solution of at least one cosmetic film forming resin.

Cosmetic resins usefully employed to produce said hair setting lotions include, for instance, polyvinylpyrrolidoue having a molecular weight ranging from about 10,000 to 700,000, copolymers of crotonic acid-vinyl acetate, for examples :90% having a molecular weight of about 45,000-50,000, copolymers of vinylpyrrolidonevinyl acetate wherein the ratio of PVP to PVA can range between, for instance, 50-70z50-30, copolymers of maleic anhydride-butylvinyl ether and the like. These resins are generally used in the proportion of l to 3% by weight of the total composition. Further, the indamine content of said hair setting lotion usually ranges between about 0.002 to 1% by weight of the total composition, preferably between 0.005-0.5 weight percent.

The alcohols suitable for making said hair setting 10- tions are lower alkanols, preferably, ethanol and isopropanol. These alcohols are used in a proportion of to 50% by weight of the total composition.

The hair setting lotion according to the invention is employed in a conventional manner by applying the same to, preferably, previously washed and rinsed, wet hair, followed by rolling the treated hair on curlers and thereafter drying it.

The present invention also relates to salts of indamines having the formula wherein R R R and R each independently represent a member selected from the group consisting of hydrogen, halogen, lower alkyl having 14 carbon atoms and lower alkoxy having l-4 carbon atoms, R represents a member selected from the group consisting of hydrogen and lower alkyl having 1-4 carbon atoms, R and R each, independently, represent a member selected from the group consisting of hydrogen, lower alkyl having 1-4 carbon atoms, hydroxy lower alkyl having 1-4 carbon atoms, amino alkyl having 1-4 carbon atoms, acylaminoalkyl wherein the alkyl moiety has 1-4 carbon atoms, morpholinoalkyl wherein the alkyl moiety has 1-4 carbon atoms and piperidinoalkyl wherein the alkyl moiety has 1-4 carbon atoms, X* is a monoor divalent anion derived from a mineral or organic acid, and particularly an anion selected from the group consisting of CH CO- Cl-, Br-, (Cl Zn) and S 0 and n is 1-2. This formula does not exclude tautomeric forms thereof.

The salts of the indamine can be obtained according to three different methods.

It is thus that, in the case where it is desired to produce a salt of an indamine where R and R each represent hydrogen one condenses a quinone diimine having the formula wherein R R R and R have the meanings given above on a 6-hydroxy phenomorpholine having the formula wherein R has the meaning given above.

Representative quinone diimines usefully employed in this condensation reaction include 2-methyl S-methoxy benzoquinone diimine, Z-methoxy 3,5-dimethyl benzoquinone diimine and 3,5-dimethoxy benzoquinone diimine.

When the salt of the indamine thus produced is not very soluble in water, the above condensation reaction can be carried out in water, either in the presence of an acid corresponding to the salt desired, or preferably in the presence of a water-soluble salt of this acid. It is thus that by condensation in an aqueous medium of a quinone diimine, above, on a phenomorpholine of above, in the presence of ammonium persulfate, there is obtained the persulfate salt of said indamine.

When, on the contrary, the salt of the indamine to be produced is very soluble in water, the condensation reaction is carried out in a solvent such as methylisobutyl ketone or dioxan in the presence of an acid corresponding to the salt desired.

In the second method of preparing the indamine salts, one condenses in an aqueous medium or a hydroacetonic medium a paraphenylene diamine having the formula wherein R R R R R and R have the meanings given above, on a 6-hydroxy phenomorpholine, defined above, this condensation reaction being carried out in the presence of a per salt, and preferably in the presence of an alkaline persulfate, such as ammonium persulfate. There is thus obtained a persulfate of the indamine which can be, in certain cases, transposed into another salt of this compound.

The third method of preparing the salts of the indamines is applicable in the situation where R and R both represent lower alkyl radicals or substituted lower alkyl radicals. This third method comprises condensing a paranitrosoaniline having the formula CIJN I No

oring characteristic in a composition having a pH ranging from 3-10. Accordingly, it is another object of the present invention to provide a composition for dyeing keratinic fibers, particularly human hair, which includes at least one of the above defined indamine salts.

The dye compositions according to the invention can include only as the active coloring agent the indamine salts in which case there is obtained, on white hair, colorations ranging from blue to green, at relatively low application times, in the order of about three minutes, at ambient temperature.

The concentration of the indamine salt in the dye compositions can vary between 0.005-1% by weight, these low concentrations being possible because of the exceptional affinity of the indamine salt for keratinic fibers.

Of course, the dye compositions of this invention containing an indamine salt can also include other dyes such as nitrophenylenediamine dyes, anthraquinone dyes, indophenols, indoanilines or other indamines.

The dye compositions of this invention impart to the keratinic fibers luminous colorations which very often are iridescent and rich in glints, thereby covering or masking the red in reddish chestnut or reddish brown hair so as to obtain deep browns with bronze green glints.

The dye compositions of the present invention containing one or more indamine salts are generally aqueous or aqueous alcoholic solutions of these salts and when an alcohol is included there is employed, preferably, ethanol although other alcohols such as butylglycol or polyoxyethylene alcohols can also be used. Additionally, the dye compositions can contain thickeners and thus be in the form of a cream or gel.

Further, the compositions of the present invention can also include various conventional ingredients usually employed in cosmetic preparations, for example wetting agents, dispersing agents, swelling agents, penetrating agents, softeners and perfumes. It has also been found that the compositions containing these indamine salts can be in the form of a sprayable aerosol, packaged in a conventional aerosol bomb or can.

The pH of the dye compositions containing one or more indamine salts can vary between 35-11 and generally between 5-9.

Dyeing of keratinic fibers, and especially human hair, with the dyeing compositions containing the novel indamine salts of this invention, is performed in accordance with conventional dyeing techniques, for instance, by applying the said composition to the fibers to be dyed, permitting the composition to remain in contact with said fibers for a period of about 3-30 minutes and thereafter, rinsing and, if desired, washing and drying the fibers.

The novel indamine salts of this invention can also be employed to provide novel hair setting lotions comprising an admixture of at least one indamine salt defined above an aqueous alcoholic solution of a cosmetic film forming resin.

Cosmetic resins usefully employed to produce hair setting lotions containing the novel indamine salts of this invention include, for instance, polyvinylpyrrolidone having a molecular weight ranging from about 10,000-700,- 000, copolyrners of crotonic acid-vinyl acetate, for instance a 190% copolymer, having a molecular weight ranging from about 45,000-50,000, copolymers of vinylpyrrolidone-vinyl acetate wherein the ratio of PVP to PVA can range between, for instance 50-70z50-30, copolyrners of maleic anhydride-butylvinyl ether and thelike. These resins are generally used in amounts of 1 to 3% by weight of the total composition. Further, the indamine salt content of said hair setting lotion can range between about 0.005-1% by weight of the total composition.

The alcohols suitable for making said hair setting 10- tions are lower alkanols, preferably, ethanol and isopropanol. These alcohols are used in amounts of about 50% by weight of the total composition.

The pH of the hair setting lotions can vary between 4-10 and preferably between 5-9.

Hair setting lotions according to the present invention which contain as a coloring agent only the above defined indamine salt impart to the hair extremely luminous colorations, rich in pearlescent and iridescent glints, a characteristic long desired in the cosmetic field. These compositions effectively mask the red in reddish chestnut or reddish brown hair, imparting thereto bronze glints.

The hair setting lotions of this invention can also include other coloring agents or dyes such as nitrophenylenediamine dyes, anthraquinone dyes, indoanilines, indophenols or other indamines.

The hair setting lotions are employed in a conventional manner by applying the same to, preferably, previously washed and rinsed, wet hair, followed by rolling the treated hair on curlers and thereafter dyeing it.

The following examples are given to illustrate the present invention. The temperatures indicated in the examples are expressed in degrees Celsius and unless otherwise specifically stated, all parts and percentages are by weight.

7' naphthyl] 2 methyl benzoquinonediimine monohydrate is prepared according to the following reaction:

a melting point of 258 Calculated for l5 l5N8 2-H20 Found Analysis, percent:

EXAMPLE 2 N-[( '6'-hydroxy 1-oxa 4'-aza 1,2',3',4'-tetrahydro) 7' naphthyl] 3-methoxy benzoquinonediimine monohydrate is prepared in accordance with the following reaction:

0.025 mole (5.27 g.) of methoxyparaphenylenediamine dichlorhydrate is dissolved in 200 cm. of water. The pH of this solution is then adjusted to a pH of 8 by adding ammonia thereto. To this alkaline solution there is immediately added 0.02 mole (3.02 g.) of 6-hydroxy phenomorpholine, previously dissolved in 200 cm. of water. To this resulting mixture there are added 90 cm. of ammonia at 22 B. and 260 cm. of 20-volurne hydrogen peroxide. This resulting reaction mixture is then permitted to stand for two hours at ambient temperature. The reaction mixture is then filtered off and there is obtained 3.8 g. of crystallized indamine in monohydrate form which, after washing with water and recrystallization in a dimethylformamide-watcr mixture, exhibits a melting point of 216.

Calculated for Cis 1sNsOa- 3O Found Analysis, percent:

C 59. 40 58. 88 59. 07 H 5. 61 5. 54 5. 52 N 13. 86 13. 80 13. 63

EXAMPLE 3 N-[(6'-l1ydroxy 1'-oxa 4'-aza l',2,3',4'-tetrahydro) 7'- naphthyl] Z-methyl S-methoxy 'benzoquinone diimine monohydrate is prepared in accordance with the following reaction:

0.03 mole (4.53 g.) of 6-hydroxy phenomorpholine is dissolved in 300 cm. of water. To this solution there are added 90 cm. ammonia at 22 B., 350 cm. of 20- volume hydrogen peroxide and 0.0375 mole (5.7 g.) of 2-methyl S-methoxy paraphenylenediamine in a solution which is a mixture of 50 cm. of water and 300 cm. of acetone. The resulting reaction mixture is allowed to stand at ambient temperature for three hours. Then 8.1 g. of crystallized indamine in monohydrate form are isolated from the reaction mixture by filtering off the same. After recrystallization in a dimethylformamide-water mixture, the product exhibited a melting point of 226.

Molecular weight calculated for C H N O -H -O: 317.

Molecular weight found by potentiometric dosing in acetic acid by perchloric acid: 323.

Analysis.-N, percent: Calculated for 13.24; found: 13.38, 13.30.

EXAMPLE 4 N-[(6'-hydroxy 1-oxa 4'-aza l',2',3',4-tetrahydro) 7'- naphthyl 2,6-dirnethyl S-methoxy] benzoquinonediimine H3 OCH;

0.02 mole (3.02 g.) of 6-hyd1'oxy phenomorpholine is dissolved in 200 cm. of water. To this solution there are added 0.025 mole (4.1 g.) of 2,6-dimethyl 5-methoxy paraphenylenediamine in solution in 200 cm. of water, cm. of ammonia at 22 B. and 250 cm. of 20-volume hydrogen peroxide. The resulting reaction mixture is allowed to stand for two hours at ambient temperature and thereafter 3 g. of crystallized indamine in monohydrate form are isolated therefrom by filtering olf the reaction mixture. After recrystallization in a dimethylformarnide-water mixture, the product exhibited a melting point of 186.

Molecular weight calculated for C H N O -H O: 331.

Molecular weight found by potentiometric closing in acetic acid by perchloric acid: 333.

Analysis.-N, percent: Calculated for C17H1QN3O3'HZOZ 12.68; found: 12. 63, 12.82.

EXAMPLE 5 N-[(6'-hydroxy 1'-oxa 4'-aza 1',2,3,4-tetrahydro) 7- naphthyl] duroquinone diimine monohydrate is prepared in accordance with the following reaction:

1 N A F A-0H H30 1 -OH:

0.005 mole (0.75 g.) of 6-hydroxy phenomorpholine is dissolved in 50 cm. of water. To this solution there are added 15 cm. of ammonia at 22 B., 0.01 mole (1.64 g.) of 1,4-diamino durene dissolved in a mixture of 30 cm. of water and 40 cm. of acetone, and finally cm. of 20-volume hydrogen peroxide. This resulting reaction mixture is allowed to stand at ambient temperature for five hours. 0.5 g. of crystallized indamine identified above in monohydrate form, is isolated by filtering off the reaction mixture. After recrystallization in a dimethylformamide-water mixture, the said indamine exhibited a melting point of 290".

Molecular weight calculated for C H N O 'H O: 329.

Molecular Weight found by potentiometric dosing in acetic acid by perchloric acid: 334.

Calculated for C mHa Ns OTHZO Found EXAMPLE 6 N-[(6'-hydroxy 4 methyl 1'-oxa 4-aza 1,2',3, '-tetrahydro) 7'-naphthyl] 3-methoxy 6-methyl benzoquinonediimine monohydrate having the following formula is prepared as follows:

To a solution of 0.0075 mole (1.70 g.) of the dihydrochloride of 2-methy1 S-methoxy paraphenylenediamine in 5 cc. of water, 7 cc. of ammonia (22 B.) and 45 cc. acetone, there is added a solution of 0.005 mole (0.825 g.) of 6-hydroxy 4-methyl phenomorpholine and finally, with agitation, 35 cc. of 20-volume H 0 The resulting reaction mixture is allowed to stand for one hour at ambient temperature. The reaction mass is then cooled to 0 C. and filtered. The resulting filtrate is washed with water and dried under vacuum, yielding 1.20 grams of crystallized indamine, above, which melts at 166 C.

Molecular weight calculated for C17H19N3O3'H2O: 331.

Molecular weight found by potentiometric dosing in acetic acid by perchloric acid: 325.

Calculated for isHnNaOz-HzO EXAMPLE 7 N-[(6-hydroxy 4'-methyl 1'-oxa 4'-aza 1',2',3',4-tetrahydro) 7-naphthyl] 3 methoxy benzoquinonediimine monohydrate having the following formula is prepared as follows:

N 44' 2,, OH 00H.

To a solution of 0.01 mole (2.11 g.) of the dihydrochloride of methoxy paraphenylene diamine in 10 cc. of water to which has been added 7 cc. of ammonia (22 B.), there is added a solution of 0.005 mole (0.825 g.) of 6-hydroxy 4-methy1 phenomorpholine in 10 cc. of acetone. Finally there are added to this mixture, with agltation, 26 cc. of 20-volume H 0 The resulting reaction mass is allowed to stand for 20 minutes at ambient temperature. It is then filtered, the filtrate washed with water and dried under vacuum yielding 0.9 g. of the above crystallized indamine which, after recrystallization in a dimethyl formamide-water mixture exhibited a melting point of 174 C.

10 EXAMPLE 8 N-[(6-hydroxy 4'-methyl 1'-oxa 4'-aza 1',2',3,4-tetrahydro) 7 naphthyl] benzoquinone diimine monohydrate having the following formula is prepared as follows:

To a solution of 0.02 mole (3.62 g.) of the dihydrochloride of paraphenylenediamine in 20 cc. of water to which has been added 7.5 cc. of ammonia (22 B.), there is added a solution of 0.01 mole (1.65 g.) of 6-hydroxy 4-methyl phenomorpholine in 10 cc. of acetone. Finally there are added, with agitation, 20 cc. of 20- volume H 0 The resulting reaction mass is allowed to stand for 30 minutes at ambient temperature and then for one hour at 0 C. The reaction mass is filtered and the filtrate washed with water and dried under vacuum, yielding 1.4 g. of the above indamine which, after recrystallization in a dimethylformamide-water mixture, exhibited a melting point of 160 C. The resulting indamine is chromatographically pure.

Molecular weight calculated for C H N O -H O: 287.

Molecular weight found by potentiometric dosing in dimethylformamide with 0.1 N isopropanol-methanol solution of tetra-n-butylammnnium hydroxide: 278.

imine monohydrate having the following formula is prepared as follows:

To a solution of 0.015 mole (3.4 g.) of the dihydrochloride of 2-methyl S-methoxy paraphenylene diamine in 10 cc. of water, cc. of acetone and 14 cc. of ammonia (22 B.), there are added 0.01 mole (2.60 g.) of the hydrobromide of 6-hydroxy 4-ethyl phenomorpholine in 5 cc. of water, 10 cc. of acetone and 3 cc. of ammonia (22 B.). Finally, to this resulting reaction mixture there are added 70 cc. of 20-volume H 0 The resulting reaction mass is allowed to stand for two hours at ambient temperature. There is then added 20 cc. of Water. The reaction mass is cooled to 0 C. and thereafter filtered, washed with water and dried, yielding 1.70 g. of the above indamine. After recrystallization in a dimethylformamide-water mixture, the indamine is chromatographically pure and exhibits a melting point of 136 C.

Molecular weight calculated for C H N O -H O: 345.

Molecular weight found by potentiometric dosing in dimethylformamide with a 0.1 N solution in isopropanolmethanol of tetra n-butylammonium hydroxide: 334.

EXAMPLE 10 The zinc and N-[6'-hydroxy 4'-methyl 1'-oxa 4-aza 1',2',3,4'-tetrahydro 7-naphthyl] N',N'-diethy1benzoquinoneimine iminium double chloride having the following formula is prepared as follows:

Into 300 cc. of absolute ethyl alcohol, there are introduced 0.03 mole (5.35 g.) of paranitrosodiethylaniline and 0.03 mole (4.95 g.) 6-hydroxy 4-rnethyl phenomorpholine. To the resulting mixture there is added 0.03 mole (4.08 g.) of anhydrous zinc chloride. The mixture is heated to reflux for 30 minutes and thereafter cooled. The precipitate formed is filtered, yielding 10.4 g. of the above indamine salt.

Zn: Percent Calculated for [C H N O ]+[Cl Zn]- 13.0 Found (determined under form of ZnO) 12.6

EXAMPLE 11 The zinc and N-[6'-hydroxy 4'-methyl 1-oxa 4'-aza 1',2,3',4 tetrahydro 7' naphthyl]N',N'-ethyl j3-piperidinoethylbenzoquinoneimine iminium double chloride hydrochloride having the following formula is prepared as follows:

Into 20 cc. of absolute ethyl alcohol, there are added 0.005 mole (1.67 g.) of the dihydrochloride of paranitroso N-ethyl N-piperidinoethylaniline and 0.005 mole (0.83 g.) of 6-hydroxy 4-methyl phenomorpholine. To this resulting mixture there is added 0.8 g. of anhydrous zinc chloride. This resulting mixture is heated to reflux for 30 minutes. After cooling, it is filtered and the resulting indamine salt washed with absolute ethyl alcohol and then with ethyl acetate. There is obtained 1.8 g. of the above indamine salt which is chromatographically pure.

EXAMPLE 12 The zinc and N-[6-hydroxy 4'-ethyl-1'-oxa 4-aza- 1',2',3',4'-tetrahydro 7-naphthyl] N',N'-ethyl p-acetylaminoethylbenzoquinoneimine iminium double chloride having the following formula is prepared as follows:

CHT'CHQ-NHCO CH EXAMPLE 13 The zinc and N-[6'-hydroxy 4'-methyl 1'-oxa 4'-aza 1',2',3',4'-tetrahydro 7'-naphthyl] N',N'-di-,8-hydroxyethylbenzoquinoneimine iminium double chloride having the following formula is prepared as follows:

Into cc. of absolute ethyl alcohol, there are added 0.005 mole (1.05 g.) of paranitroso-N,N-di-B-hydroxyethylaniline and 0.05 mole (0.83 g.) of G-hydroxy 4-methyl phenomorpholine. To this resulting mixture there is added 0.8 g. of anhydrous zinc chloride. The mixture is heated to reflux, with agitation, for 30 minutes. After cooling, it is filtered and the thus isolated salt is washed with absolute ethyl alcohol, yielding 2.30 g. of the above indamine salt which is chromatographically pure.

EXAMPLE 14 The zinc and N-['6-hydroxy 4'-ethyl 1-oxa 4'-aza 1',2',3',4'-tetrahydro 7-naphthyl] N,N'-di-p-hydroxyethylbenzoquinoneimine iminium double chloride having the following formula is prepared as follows:

Into 20 cc. of absolute ethyl alcohol there are introduced 0.005 mole (1.05 g.) of paranitroso-N,N-di-/3-hydroxyethylaniline and 0.005 mole (0.90 g.) of 6-hydroxy 4-ethyl phenomorpholine. To this resulting mixture there is added 0.8 g. of anhydrous zinc chloride. The resulting mixture is heated to reflux, with agitation, for 30 minutes. After cooling the above indamine salt is recovered by filtration and washed with absolute ethyl alcohol, yielding 2.25 g. thereof which is chromatographically pure.

EXAMPLE 15 The acetate of N-[6-hydroxy 1'-oxa 4'-aza l,2',3',4'- tetrahydro 7'-naphthyl] B-methoxy 6 methyl benzoquinoneimine iminium having the following formula is prepared as follows:

0.005 mole (0.75 g.) of 2-methy1 S-methoxy benzoquinonediimine is dissolved in 13 cc. of methylisobutyl ketone. To this solution there is added 0.005 mole (0.755 g.) of 6-hydroxy phenomorpholine in 10 cc. of methyl isobutylketone to which has been added 0.3 cc. of acetic acid. Shortly thereafter the resulting reaction mixture is filtered to isolate the above indamine salt, which after washing with methylisobutylketone and drying yields 0.42 g. of the said salt which is chromatographically pure.

Molecular weight calculated for C H N O 359 Molecular weight found by potentiometric dosing in acetic acid with perchloric acid 345 EXAMPLE 16 The acetate of N-[6'-hydroxy 4'-methyl 1-oxa 4'-aza 1',2',3',4'-tetrahydro 7-naphthyl] 3 methoxy 6 methyl benzoquinoneimine iminium having the following formula is prepared as follows:

0.005 mole (0.75 g.) of Z-methyl S-methoxy benzoquinonediimine is dissolved in 13 cc. of methylisobutyl ketone. To this solution there is added 0.005 mole (0.83 g.) of 6-hydroxy 4-methyl phenornorpholine in 10 cc. of methylisobutyl ketone to which has been added 0.3 cc. of acetic acid. Shortly thereafter the precipitate formed is filtered, washed with a little methylisobutyl ketone and dried, thus yielding 0.40 g. of the above indamine salt.

EXAMPLE 17 The persulfate of N-[6'-hydroxy 1-oxa 4'-aza 1',2',3', 4'-tetrahydro 7'-naphthyl] I l-methoxy 2,6-dimethyl benzoquinoneimine iminium is prepared as follows:

CHaCOr A first solution is prepared by dissolving 0.005 mole (0.75 g.) of 6-hydroxy phenomorpholine in 20 cc. of acetone. A second solution is prepared by dissolving 0.0075

mole (1.8 g.) of the dihydrochloride of 2-methoxy 3,5

dimethyl paraphenylenediamine in 10 cc. of water to which has been added 1.5 cc. of ammonia (22 B.). The two solutions are cooled and mixed and to the resulting mixture there is added 2.28 g. of ammonium persulfate dissolved in 20 cc. of water. The precipitate formed,

which is the above indamine salt, is filtered, washed with a little ice water and then with a little acetone and finally dried, yielding 0.7 g. of the above indamine salt which is chromatographically pure.

EXAMPLE 18 The persulfate of N-[6'-hydroxy 4-methyl 1-oxa 4'- aza 1',2',3',4'-tetrahydro 7-naphthyl] S-methoxy 2,6-dimethyl benzoquinoneimine iminium is prepared as follows:

0.005 mole (0.82 g.) of 2,6-dimethyl 3-methoxy benzoquinonediimine is dissolved in 11 cc. of ice water. To this solution there are immediately added 0.005 mole (0.83 g.) of 6-hydroxy 4-methyl phenomorpholine in 3 cc. of acetone and 1.5 g. of ammonium persulfate dissolved in 4.5 cc. of water. The resulting precipitate is filtered off, washed with a little ice water and then with some acetone, yielding 0.65 g. of the above indamine salt.

EXAMPLE 19 A hair dye composition, in accordance with invention, is prepared as follows:

G. The indamine of Example 2 0.1 Lauryl alcohol oxyethylenated with 10.5 moles of ethylene oxide 5 Water suflicient for 100 g.

This dyeing composition solution is applied to 90% gray hair and left in contact therewith for 30 minutes. The hair is then rinsed and shampooed. A green gray shade is obtained.

EXAMPLE 20 A hair setting lotion, in accordance with the present invention, is prepared as follows:

Indamine of Example 2 0.1

Crotonic acid-vinyl acetate copolymer =(10%:90%,

mol. wt. 45,000)

Ethanol-96 titer sufficient for 50. Water sufiicient for 100 g.

This hair setting lotion is applied to 100% white hair and imparts thereto a dull green hue.

EXAMPLE 21 A hair setting lotion is prepared as follows:

G. The indamine of Example 5 0.1 Crotonic acid-vinyl acetate copolymer (10%:90%,

mol. wt. 45,000 2 Isopropanol sufiicient for 50.

Water sutlicient for 100 g.

This hair setting lotion is applied to 100% white hair and imparts thereto a golden blond color.

EXAMPLE 22 A hair dye composition is prepared as follows:

G. The indamine of Example 4 0.2 Butylglycol 5 Lauryl alcohol oxyethylenated with 10.5 moles of ethylene oxide 5 Water sufficient for 100 g.

EXAMPLE 23 A hair dye composition is prepared as follows:

G. The indamine of Example 4 0.1 N[(4-amino 3' methyl)phenyl] 3-amino 2,6-dimethyl benzoquinoneimine 0.1 Ammonia sufiicient for pH 10.5.

Water sufficient for 100 g.

This hair dye composition is applied to White hair and permitted to remain in contact therewith for a period of about 30 minutes. The hair is then rinsed and shampooed and a clear chestnut coloring with slight violet glints is imparted thereto.

EXAMPLE 24 A hair setting lotion is prepared as follows:

' G. The indamine of Example 3 0.2 Crotonic acid-vinyl acetate copolymer (10%:90%,

mol. wt. 50,000) Ethanol-96 titer, sufiicient for 5 0. Water sufficient for 100 g.

This hair setting lotion is applied to bleached hair and imparts thereto a blond color with Cyprian green glints.

EXAMPLE 25 The following solution is prepared:

G. The indamine of Example 7 0.05 Crotonic acid-vinyl acetate copolymer (10%:90%,

M.W. 50,000) 2 Ethyl alcohol-96 titer 50 Water q.s.p-- 100 Triethanolamine, q.s.p. pH 7.

This hair setting lotion is applied to bleached hair and imparts thereto a pale green coloration with golden glints.

EXAMPLE 26 The following solution is prepared:

G. The indamine of Example 7 0.2 Ethanol, 96 titer 3 Water q.s.p. 100 Ammonia (22 B.), q.s.p. pH 7.

This solution is applied to bleached hair and is permitted to remain in contact therewith for 20 minutes. After rinsing and shampooing the thus treated hair, there is imparted thereto a golden blond coloring with green glints.

EXAMPLE 27 The following solution is prepared:

G. The indamine of Example 6 0.3 Ethanol, 96 titer 50 Water q s p 100 Ammonia (22 B.), q.s.p. pH 10.5.

This solution is applied to naturally white hair and is permitted to remain in contact therewith for 20 minutes. After rinsing and shampooing a pale, silvery green coloration is imparted thereto.

EXAMPLE 28 The following solution is prepared:

G. The indamine of Example 6 0.1 Crotonic acid-vinyl acetate copolymer (10%:90%,

M.W. 45,000-50,000) Ethanol, 96 titer, q.s.p. 50.

Water q.s.p.-- 100 Triethanolamine, q.s.p. pH 7.

The following solution is prepared:

G. The indamine of Example 6 0.4 Ethanol, 96 titer, q.s.p. 50. Water q.s.p. 100

Lactic acid (10% solution). q.s.p. pH 4.

This solution is applied to 95% naturally white hair and is permitted to remain in contact therewith for minutes. After rinsing and shampooing, a pearlescent coloration with very pale luminous green glints is imparted thereto.

EXAMPLE 30 The following solution is prepared:

G. The indamine of Example 6 0.1 N [(2',4' diamino 5 methoxy) phenyl] benzoquinoneimine 0.05 Ethanol, 96 titer 50 Water q.s.p 100 Triethanolamine, q.s.p. pH 7.

This solution is applied to bleached hair and is permitted to remain in contact therewith for minutes. After rinsing and shampooing, there is imparted to the hair a very light iridescent reddish golden coloration.

EXAMPLE 31 The following solution is prepared:

G. The indamine of Example 8 0.1 Crotonic acid-vinyl acetate copolymer (10%:90%,

M.W. 45,000-50,000) 2 Ethanol, 96 titer, q.s.p. 50.

Water q.s.p. 100 Triethanol amine, q.s.p. pH 7.

This hair setting lotion is applied to bleached hair and imparts thereto a golden coloration with pale green glints.

EXAMPLE 32 The following solution is prepared:

G. The indamine of Example 8 0.4 Butyl glycol 5 Lauryl alcohol oxyethylenated with 10.5 moles ethylene oxide 5 Water q.s.p. 100 The pH of this solution is 7.

This solution is applied to 95% naturally white hair and is permitted to remain in contact therewith for 20 minutes. After rinsing and shampooing, a light bronze coloration is imparted thereto.

EXAMPLE 33 The following solution is prepared:

G. The indamine of Example 6 0.2 N [(4 hydroxy phenyl] 2,6 dimethyl benzoquinoneimine 0.05 Ethanol, 96 titer Water q.s.p 100 Ammonia (22 B.), q.s.p. pH 10.

This solution is applied to 95% naturally white hair and is permitted to remain in contact therewith for 20 minutes. After rinsing and shampooing, a beige coloration with rosewood glints is imparted thereto.

EXAMPLE 34 The following solution is prepared:

The indamine of Example 8 0.15 N-[(4-amino)phenyl] 3-amino 6-methyl benzoquinoneimine 0.05 Ethanol, 96 titer, q.s.p., 35. Water q.s.p 100 Ammonia (22 B'), q.s.p., pH 8.

This solution is applied to bleached hair and is permitted to remain in contact therewith for 20 minutes. After rinsing and shampooing, a very luminous pearlescent blond coloration is imparted thereto.

EXAMPLE 35 The following solution is prepared:

The indamine of Example 8 0.10 The acetate of N-[(4'-amino Z-methoxy 5'-methyl)phenyl] 3-amino 6-methyl benzoquinonediimine 0.025

Safranine 0.0125

Ethanol, 96 titer 25 Water q.s.p 100 Ammonia (22 B), q.s.p., pH 7.

This solution is applied to naturally white hair and is permitted to remain in contact therewith for 10 minutes. After rinsing and shampooing, a light blue coloration with silvery glints was imparted thereto.

EXAMPLE 36 The following solution is prepared:

The indamine of Example 8 0.15 The hydrochloride of l-methyl 18-aminoethylamino 3-nitro 4-methylamino benzene 0.15 Crotonic acid-vinyl acetate copolymer (10%:90%,

Ethanol, 96 titer 50 Water q.s.p 100 Triethanolamine, q.s.p., pH 7.

This hair setting lotion is applied to bleached hair and imparts thereto a pearlescent, purplish, light chestnu coloration.

Triethanolamine, q.s.p., pH 7.

This hair setting lotion is applied to bleached hair and imparts thereto a light ashen chestnut coloration having a pearlescent effect.

EXAMPLE 38 The following solution is prepared:

G. The indamine of Example 9 0.05 Crotonic acid-vinyl acetate copolymer (10%:90%,

Ethanol, 96 titer, q.s.p., 50. Triethanolamine, q.s.p., pH 7.

This hair setting lotion is applied to bleached hair and imparts thereto a pearlescent almond green coloration.

17 EXAMPLE 39 The following solution is prepared:

The indamine salt of Example 0.05 Crotonic acid-vinyl acetate copolymer (10% :90%,

Ethyl alcohol, 96 titer 50 Water q.s.p 100 T riethanolamine, q.s.p., pH 7.

This hair setting lotion is applied to 95% white hair and imparts thereto a forget-me-not blue coloration with very silvery glints.

EXAMPLE 40 The following solution is prepared:

G. The indamine salt of Example 10 0.2 Nitroparaphenylene diamine 0.05 Ethyl alcohol, 96 titer 20 Water q.s.p 100 Ammonia (22 B.), q.s.p., pH 9.

This solution is applied to 95% naturally white hair and is permitted to remain in contact therewith for 20 minutes at ambient temperature. After rinsing and shampooing the hair, there is imparted thereto a light pearlescent chestnut coloration.

EXAMPLE 41 The following solution is prepared:

G. The indamine salt of Example 11 0.05 Crotonic acid-vinyl acetate copolymer (10%:90%, M.W. 45,00050,000) Ethyl alcohol, 96 titer, q.s.p., 50. Water q.s.p 100 Triethanolamine, q.s.p., pH 7.

This hair setting lotion is applied to bleached hair and imparts thereto a foret-me-not blue coloration with silver glints.

EXAMPLE 42 The following solution is prepared:

G. The indamine salt of Example 11 0.15 N [(4' hydroxy)phenyl] 2,6-dimethyl benzoquinoneimine 0.25 Ethyl alcohol, 96' titer 25 Water ..q.s.p 100 Ammonia (22 B.), q.s.p., pH 9.5.

This solution is applied to 95% naturally white hair and is permitted to remain in contact therewith for 20 minutes. After rinsing and shampooing, there is imparted to the hair a silver gray coloration.

EXAMPLE 43 The following solution is prepared:

G. The indamine salt of Example 11 0.10 Ethyl alcohol, 96 titer 25 Water q.s.p.. 100

Ammonia (22 B.), q-s.p., pH 9.

This solution is applied to 95% naturally white hair and is permitted to remain in contact therewith for 20 minutes. After rinsing and :sh ampooing, there is imparted to the bald a deep silver blue coloration.

18 EXAMPLE 44 The following solution is prepared:

G. The indamine salt of Example 11 0.1 N-[2',4' diamino 5-methoxy) phenyl] benzoquinoneimine 0.2 Ethyl alcohol, 96 titer 25 Water q.s.p 100 Ammonia (22 B.), q.s.p. pH 10.

This solution is applied to naturally white hair and is permitted to remain in contact therewith for 20 minutes. The hair is then rinsed and washed and there is imparted thereto a rosewood coloration.

EXAMPLE 45 The following solution is prepared:

G. The indamine salt of Example 12 0.1 Crotonic acid-vinyl acetate copolymer (10%:90%, M.W. 45,000-50,000) Isopropyl alcohol, q.s.p. 50". Water q.s.p

Triethanolamine, q. s .p. pH 7.

This hair setting lotion is applied to bleached hair and imparts thereto a silver blue coloration.

EXAMPLE 46 The following solution is prepared:

G. The indamine salt of Example 12 0.1 Water q.s.p 100 This solution, which has a pH of 7 is applied to 95 naturally white hair and is permitted to remain in contact therewith for 20 minutes. The hair is then rinsed and shampooed and there is imparted thereto a blue gray coloration.

EXAMPLE 47 The following solution is prepared:

G. The indamine salt of Example 12 0.2 Water q.s.p 100 Lactic acid (10% solution), q.s.p. pH 4.

This solution is applied to 95% naturally white hair and is permitted to remain in contact therewith for 10 minutes. The hair is then rinsed and shampooed and there is imparted thereto a silver gray coloration with light green glints.

Triethanolamine, q.s.p. pH 7.

This hair setting lotion is applied to bleached hair and imparts thereto a light violet coloration with pearlescent glints.

EXAMPLE 49 The following solution is prepared:

The indamine salt of Example 13 0.04 N-[2,4' diamino 5' methyl)phenyl]benzoquinoneimine 0.05 Nitropanaphenylene diamine 0.04 Ethyl alcohol, 96 titer, q.s.p. 40. Water q.s.p 100 Ammonia (22 B.), q.s.p. pH 10.

19 This solution is applied to 95% naturally white hair and is permitted to remain in contact therewith for 20 minutes. The hair is then rinsed and shampooed and there is imparted thereto a light cinderash chestnut coloration with purplish glints.

EXAMPLE 50 The following solution is prepared: G The indamine salt of Example 13 0.05 N-[ (4' hydroxy)phenyl]3 amino 6-methyl benzoquinoneimine 0.20 Nitroorthophenylenediamine 0.10 Crotonic acid-vinyl acetate copolymer (10%:90%,

M.W. 45,000-50,000) 2 Isopropyl alcohol, q.s.p. 50".

Water .q.s.p 100 Triethanolamine, q.s.p. pH 7.

This hair setting lotion is applied to bleached hair and imparts thereto a light golden bronze coloration.

EXAMPLE 51 The following solution is prepared:

G. The indamine salt of Example 14 0.05 Crotonic acid-vinyl acetate copolymer (10%:90%,

M.W. 45,000-50,000) Ethanol, 96 titer, q.s.p. 50.

Water q.s.p 100 Triethanolamine, q.s.p. pH 7.

This hair setting lotion is applied to bleached hair and imparts thereto a very luminous silver blue coloration.

EXAMPLE 52 The following solution is prepared:

G. The indamine salt of Example 15 0.1 Crotonic acid-vinyl acetate copolymer (10%90%,

45,000 Isopropyl alcohol, q.s.p. 50. Water q.s.p 100 Triethanolamine, q.s.p. pH 7.

This hair setting lotion is applied to bleached hair and imparts thereto a very luminous deep blue coloration.

EXAMPLE 53 The following solution is prepared:

G. The indamine salt of Example 15 0.02 Water q.s.p-- 100 Ammonium (22 B.), p.s.-p. pH 10. 55

This solution is applied to 95% naturally white hair and is permitted to remain in contact therewith for 3 minutes. The hair is then rinsed and shampooed and there is imparted thereto a light blue green coloration with silver glints.

EXAMPLE 54 The following solution is prepared:

G. The indamine salt of Example 15 0.025 N-[(2,4' diamino 5' methoxy)phenyl]benzoquinoneimine 0.1 Crotonic acid-vinyl acetate copolymer (10% M.W. 45,000) 2 Isopropyl alcohol 50 70 Water q.s.p-.. 100 Triethanolamine, q.s.p. pH 7.

This hair setting lotion is applied to bleached hair and imparts thereto a pearlescent blue gray coloration. 7

Triethanolamine, q.s.p, pH 7.

This hair setting lotion is applied to bleached hair and imparts thereto a very deep chestnut coloration with bronze green glints.

EXAMPLE 56 The following solution is prepared:

G. The indamine salt of Example 16 0.05 Crotonic acid-vinyl acetate copolymer (10%:90%,

M.W. 50,000) Isopropyl alcohol 50 Water q.s.p 100 Triethanolamine, q.s.p, pH 7.

This hair setting lotion is applied to naturally white hair and imparts thereto an emerald green coloration.

EXAMPLE 57 The following solution is prepared:

G. The indamine salt of Example 16 0.5 Isopropyl alcohol 20 Water q.s.p

Lactic acid (1% solution), q.s.p. pH 5.

This solution is applied to 95% naturally white hair and is permitted to remain in contact therewith for 20 minutes. The hair is then rinsed and shampooed and there is imparted thereto a very luminous blue green coloration.

EXAMPLE 58 The following solution is prepared:

The indamine salt of Example 17 0.05 Crotonic acid-vinyl acetate cooplymer (10%:90%,

Ethyl alcohol, 96 titer 50 Water q.s.p-- 100 Triethanolamine, q.s.p. pH 7.

This hair setting lotion is applied to bleached hair and imparts thereto a periwinkle blue coloration with iridescent glints.

EXAMPLE 59 The following solution is prepared:

- G. The indamine salt of Example 18 0.15 Crotonic acid-vinyl acetate copolymer (10%:90%,

M.W. 50,000) 2 Ethyl alcohol, 96 titer 50 Water q.s.p 100 Triethanolamine, pH 7.

This hair setting lotion is applied to bleached hair and imparts thereto a very iridescent deep blue coloration.

EXAMPLE 60 The following solution is prepared:

The indamine salt of Example 18 0.2

Butylglycol 5 Lauryl alcohol oxyethylenated with 10.5 moles ethylene oxide 5 Water q.s.p 100 This solution is applied to 95% naturally white hair and is permitted to remain in contact therewith at ambient temperature for 20 minutes. The hair is then rinsed and shampooed and there is imparted thereto a light bluish green coloration.

EXAMPLE 61 The following solution is prepared:

G. The indamine of Example 1 0.2 Crotonic acid-vinyl acetate copolymer (10% :90%,

mol. wet, 50,000) 2 Ethanol-96 titer, suflicient for 50. Water, suflicient for 100 g.

This hair setting lotion is applied to bleached hair and imparts thereto a light cinderash blond coloration with lime glints.

EXAMPLE 62 The following solution is prepared:

G. The indamine of Example 4 0.2

N-[(4 hydroxy) phenyl] 3-acetylamino 6-methyl benzoquinoneimine Ammonia (22 B), sufiicient for pH 10.

Water, suflicient for 100 g.

This solution is applied to 95% naturally white hair and is permitted to remain in contact therewith for 30 minutes. After rinsing and shampooing, a cinderash blond with light pink glints was imparted thereto.

What is claimed is:

1. A keratinous fiber dyeing composition comprising a solution of at least one compound having the formula wherein R R R and R each independently represent a member selected from the group consisting of hydrogen, halogen, lower alkyl having 14 carbon atoms and lower alkoxy having 14 carbon atoms and R represents lower alkyl having 14 carbon atoms in a solvent selected from the group consisting of water and an aqueous solution of a lower alkanol selected from the group consisting of ethanol and isopropanol, the above formula not excluding the tautomeric forms thereof.

2. The composition of claim 1 wherein the pH of said composition ranges between 4-11 3. The composition of claim 2 wherein the pH ranges between 7-11.

4. The composition of claim 1 wherein said compound is present in an amount ranging between about 0.002 to 1 percent by weight of the total composition.

5. The composition of claim 4 wherein said compound is present in an amount ranging between 0.005 to 0.5 percent by weight of the total composition.

6. The composition of claim 1 wherein said solvent is said aqueous solution of said lower alkanol and wherein said solution further contains a film forming resin in amounts of about 1-3 weight percent based on the weight of said composition.

7. The composition of claim 1 wherein the solvent is water and which also includes a member selected from the group consisting of butylglycol and polyoxyethylenated lauryl alcohol.

8. The composition of claim 1 wherein the alcohol is present in amounts ranging from about 20-50 percent by weight of said composition.

9. The composition of claim 1 wherein said solution further contains another dye selected from the group consisting of indoaniline, indophenol, nitrophenylene diamine and mixtures thereof.

22 '10. A keratinous fiber dyeing composition comprising a solution of at least one compound having the formula wherein R R R and R each, independently, represent a member selected from the group consisting of hydrogen, halogen, lower alkyl having 1-4 carbon atoms and lower alkoxy having 14 carbon atoms, R represents a member selected from the group consisting of hydrogen and lower alkyl having 1-4 carbon atoms, R and R each, independently, represent a member selected from the group consisting of hydrogen, lower alkyl having 1-4 carbon atoms, hydroxy lower alkyl having 14 carbon atoms, aminoalkyl having 1-4 carbon atoms, acylaminoalkyl wherein the alkyl moiety has 1-4 carbon atoms, morpholinoalkyl wherein the alkyl moiety has 1-4 carbon atoms and piperidinoalkyl wherein the alkyl moiety has 14 carbon atoms, X is an anion derived from an acidic material selected from the group consisting of mineral acid, organic acid and water-soluble salts thereof and n is 1-2, the above formula not excluding the tautomeric forms thereof, in a solvent selected from the group consisting of water and an aqueous solution of a lower alkanol selected from the group consisting of ethanol and isopropanol.

11. The composition of claim 10 wherein said compound is present in amounts of 0.005-1 percent by weight of said composition. 1

12. The composition of claim 10 having a pH ranging between 3-10.

13. The composition of claim 10 wherein said solvent is said aqueous solution of said lower alkanol, wherein said solution further contains a film forming resin in amounts of about 1-3 weight percent based on the weight of said composition.

14. The composition of claim 10 wherein said alcohol is present in amounts ranging from about 20-50 percent by weight of said composition.

15. The composition of claim 10 wherein said solution further contains another dye selected from the group consisting of indoaniline, indophenol, nitrophenylene diamine and mixtures thereof.

16. The composition of claim 10 wherein the solvent is water and which also includes a member selected from the group consisting of butylglycol and polyoxyethylenated lauryl alcohol. 17. A process for dyeing keratin fibers which comprises applying to said fibers in an amount effective to dye the same a solution in a solvent selected from the group consisting of water and an aqueous solution of a lower alkanol selected from the group consisting of ethanol and isopropanol of a dye having the formula V wherein R R R and R each, independently, represent a member selected from the group consisting of hydrogen, halogen, lower alkyl having 1-4 carbon atoms and lower alkoxy having 1-4 carbon atoms, and R represents lower alkyl having l-4 carbon atoms, the above formula not excluding the tautomeric forms thereof, in amounts of about 0.0021 percent by weight of said solution, permitting said composition to remain in contact with said fibers for a period ranging from about 5-30 minutes,

rinsing said fibers, eventually washing said fibers and drying said fibres.

18. The process of claim 17 wherein the solvent is water and which also includes a member selected from the group consisting of butylglycol and polyoxyethylenated lauryl alcohol.

19. A process for dyeing keratin fibers which comprises applying to said fibers in an amount efiective to dye the same a solution in a solvent selected from the group consisting of water and an aqueous solution of a lower alkanol selected from the group consisting of ethanol and isopropanol of a dye having the formula wherein R R R and R each, independently, represent a member selected from the group consisting of hydrogen, halogen, lower alkyl having 1-4 carbon atoms and lower alkoxy having 14 carbon atoms, R represents a member selected from the group consisting of hydrogen and lower alkyl having 1-4 carbon atoms, R and R each, independently, represent a member selected from the group consisting of hydrogen, lower alkyl having 1-4 carbon atoms, hydroxy lower alkyl having 1-4 carbon atoms, aminoalkyl having, 1-4 carbon atoms, acylaminoalkyl wherein the alkyl moiety has 1-4 carbon atoms, morpholino-alkyl wherein the alkyl moiety has 1-4 carbon atoms and piperidinoalkyl wherein the alkyl moiety has l-4 carbon atoms, X- is. an anion derived from an acidic material selected from the group consisting of mineral acid, organic acid and water soluble salts thereof and n is 1-2, the above formula not excluding the tautomeric forms thereof, in amounts of about 0.005-1 percent by weight of said solution, permitting said composition to remain in contact with said fibers for a period ranging from about 3-30 minutes, rinsing said fibers, eventually washing said fibers and drying said fibers.

20. A process for coloring and setting hair comprising washing and rinsing said hair and then applying to said hair in amounts effective to color and set said hair, a hair setting lotion comprising a solution in an aqueous lower alkanol solvent wherein said lower alkanol is selected from the group consisting of ethanol and isopropanol of a dye having the formula wherein R R R and R each independently, represent a member selected from the group consisting of hydro- 24 gen, halogen, lower alkyl having 1-4 carbon atoms and lower alkoxy having 14 carbon atoms and R represents lower alkyl having l-4 carbon atoms, the above formula not excluding the tautomeric forms thereof, in amounts of about 0.005-1 percent by weight of said lotion, and a film forming resin in amounts of about 1-3 percent by weight of said lotion, setting said hair in the desired configuration and drying said hair.

21. A process for coloring and setting hair comprising washing and rinsing said hair and applying to said hair in amounts eifective to color and set said hair, a hair setting lotion comprising a solution in an aqueous lower alkanol solvent wherein said lower alkanol is selected from the group consisting of ethanol and isopropanol of a dye having the formula wherein R R R and R each, independently, represent a member selected from the group consisting of 'hydrogen, halogen, lower alkyl having l-4 carbon atoms and lower alkoxy having 1-4 carbon atoms, R represents a member selected from the group consisting of hydrogen and lower alkyl having 1-4 carbon atoms, R and R each, independently, represent a member selected from the group consisting of hydrogen, lower alkyl having 1-4 carbon atoms, hydroxy lower alkyl having l-4 carbon atoms, aminoalkyl having 1-4 carbon atoms, acylamino alkyl wherein the alkyl moiety has 14 carbon atoms, morpholinoalkyl wherein the alkyl moiety has 1-4 carbon atoms and piperidinoalkyl wherein the alkyl moiety has 1-4 carbon atoms, X is an anion derived from an acidic material selected from the group consisting of mineral acid, organic acid and water-soluble salts thereof and nis 1-2, the above formula not excluding the tautomeric forms thereof, in amounts of about 0.005-1 percent by weight of said lotion and a film forming resin in amounts of about 1-3 percent by weight of said lotion, setting said hair in the desired configuration and drying said hair.

References Cited UNITED STATES PATENTS 3,482,923 12/1969 Boosen et al. 8-10 X 3,088,877 5/1963 Brunner et al. 8-10 X 2,364,347 12/ 1944 Dickey et a1. 260-247 GEORGE F. LESMES, Primary Examiner P. C. IVES, Assistant Examiner US. Cl. X.R. 

